Process of treating petroleum oils



Sept. 1, 1925.

Filed Au; l5. 1922 ,aa/a

Patented Sept. 1, 1925.

N UNITED -,sTATfEs- PATENT j .OFFICES n ICHAnn F. DAvIs, or EL SEGUNDWCALIFCBNIA, AssIGNonrosmANnAnn' on. Cou- PANY, or SAN rItANCIsco, CALIFORNIA, A Conro-RA'rIoN or CALIFORNIA.

- rnoCEss or mnnA'rINC PETROLEUM o'ILs.l f

Application nica August-15, 1922. -serm no isnsaf j (j To all whom-it, may concern:

Be it-known that I, RICHARD- a citizen ofthe United States, residing at El Segundo, in the county of Los Angeles and State of California, lrave invented a new and useful Process of Treating Petroleum 'Oils,' of which the following is'a specification.

This invention relates to a process of treating distillatesA which have been obtained from the cracking or destructive distillation of petroleum oils, and while not necessarily confined thereto, refers more particularly toY the treatment of thecracked distillates from California or asphaltic basenrudes.

Distillates which are obtainedfrom cracking or destructive distilling operations differ materially from the natural distillates obtained from the same oil. These distillates are generally more unsaturated, that is, contain `more unsaturated a d unstable constituents, contain larger per entages of gum and vitarry material and present to the reiner a problem which is diiicult if at all niet by such processes as are now in use. To refine these distillates in the customary manner, with sulphuric acid, requires a large quantity of sulphuric acid and involves a large loss of the distillates. y

I have discovered that this loss Vof de-l sirable distillatesI and the use of acidI canbe minimized and a much more desirableproduct obtainedfby 4treating these distillates in a process'which will be herein described.

Generally, the object of this'invention is to produce a motor rfuel from distillates obtained in a cracking process, which` motor v fuelwill pass all quality land stability 'tests speciied 1n the Bureau of Mines Bulletin No'. 305. i

An object of this invention is produce amore economical process for refining these` distillates. l

. Specically, the objects of this invention I are: (1st) to.mnimize'the use of sulphfuxic acid; (2nd) tov minimize refining losses; (3rd) to remove Vorganic acids, both those inherent in the distillate and resulting intermediate` in the process; (4) to' remove all the easily oxidizable materials; (5th) to remove the constituents inl the distillate which dissolve metal; (6th) to improve the color; (7th) to stabilize the oily so that it will not tend to form gums or acquire color A l(8th) to employ acontrollable oxidation in F. DAvfs,

place of `the action of'sulphuricfacidkand (9th) to provide a process Vwllh;l may be conducted in the equlpment in ordinary use at a reinery without necessitating lexpensive changes in that equipment; o v have found that'bytreating the'sejdistillates wlth Copper oxide, the undesirable constituents unite with the copper oxide to form oil soluble material which may be separated from the oil, leaving the oilin ahighly refV fined and suitable condition', by simple disftillation of the oil. from these compoundsw- The action of the copper oxide on these ymaterials 1s greatly accelerated if not de-` pendent upon the presence of light which may be diffused daylight, sun-,light or artiw ganic acids which acty with the metal oxide forming corresponding metal salts.y The -icial light, .preferably containing .ahigh treatment with copper oxide can be carried `out on the cold oil by agitating the oil with finely divided copper oxide, whereby suiicient of the copper oxide will dissolved in the oilxtounite with those constituents undesirable in ahigh quality ofmotor fuel and. i that the oil containing the dissolved copper" may then be readily separated'by decantation or other means, whereby only4 the copper oxide which is essential tothe treatment will be consumedVv and the remaining oxide will' be maintained in a condition properjnforV further treating said distillate.

y processus eatly facilitated by the;faction'V i of light, an produces/results entirely different from those of the prior processes.A ItY is especially 'to be noted that these rior processesare 'conducted only upon sunk oils for the removal of'sulphu'r., In my process there is no material reduction in' 1 the sulphurl content by ithe` copper loxide treatment.

My process should notbe confusedwith'/ some ofthe olderprocesses .which treat-nor-`4 mal paraiiine base distillates, whichcontainQ alarge percentage of sulphur and are called' 95 shunk oils, land are employedfor the moval of sulphur. The action of coppeli.

I `have further discovered that this copper oxide'treatment may be materially aided by u first treating the distillate with a-small quan-i of my process.

' Referring to .the drawingfrepresentsan agitating tank whichgis preferably either open at the topl or closed with lass or other light diffusing material. 1 in ioates an oil rcharging line, 9 indicatesadraw-olf llne' connecting to thebottom of said agitating tank. A' conveyor iis4 provided, connected toa supply of copper oxide (notshown), which Aleadsto the agitating tank 2. Said r tank 2 is provided with a swlngpipe 4 which is connected by aline 5 lcontaining a valve. 21 to' a pump 6. The pum Av6- is connected through a T-connection 22, rstthrough the line. 25 containing the valve 7 to a perforated" line v48, in the agltating tank 2; and second, l thr ugh a line 'containing-,valves 231`and a steamcoil' 26 connected by 4aline27 to a source'of steam. The vaporline of the still v11 lea s 'to a condensercoil 13 `surrounded by a condenser box 16; Thecondenser coil 4. 3

543 is connected by a lineflfto a receivi f tank 18.` The` condenser boxtgl is provid .with a line 14 connectedto a/source of water (not shown) for supplyinggcoolin water to the condenser coil 13 and 'said con enser box 40 "'16 -is further provided `with a How olf line f f 15, through'which, the-water is discharged.v

- In operationof theprocessthe distillate -before or aften, such preliminary treatment, as will belaterkdescribed, is'introduced into the agitatingtank 2`throughfthe line l. A

' copper oxide referred to in this specification suitable quantity -linely 'divided copper oxide 'is supplied the conveyor 3. The

s is preferably cupric oxidef Valve -23 is closed, valves 21 and 7 ane opened and the copperyoxide and.' distillate are agitated by circulation through the lines ,41, 5, 25 and 8 by operation of the 'pum 6. This agitation `is continued until all t e undesirable constituents have .united with-the acopper oxide forming oil soluble constituents. Light enters through the'top of theagitating tankv l h 2-and materially aidsin thev oxidizlng or photo-chemical action. n j, t

The contents of the agitating tank 2 'are allowed to settle and then pumped by the pump 6 to the still 11, valves 21, 23,24-1being l open and the valve 7 being closed.- The oil drawing,` illustrating diiagrammatically van apparatus for conducting copper oxide steps ascii 11. The stili-11 liS-p-mvided l 4 ilyserve to remove a large portion o with aI draw-`ofline 20; avaporline 12 and much -tweake acid. Preferably I addto a gallon of oil 1A of a pound of 58 Baume sul- -whicn ,includes f su tillates, in the presence of oxide untilthe resultant actioniscomplete, and separating theoil `from'theundissolved oxide and the dissolved copper compounds.'

is theirdistilled fnom'the solublecopper com.-`

'65 pounds byfany ,of` the usual heating means, which includes removing "t theline 27 and `coil 26.' The vaporspa'ssing through the vapor line 12 are condensed in` A the 'coilsl and pass to the storage tank 18. The distillate AWill then berfound to of vegl high quality t Y 't Y `eprehminary treatment of the distillate before referred to maybe conducted in-a 'number o'f different ways andhas a marked effect u on the copper oxide treatment., The` ently to remove the sulphur constituents of the oil. In general thereare two manners' in which` this preliminary-treatment maybe conducted. f`

In the rst method, the"distillate'i`s'treat ed with caustic soda; the caustic soda sepa:` rated from the oil and the oil with a small amount of concentrated ory fum-` ing sulphuric acid. 'The acid sludge isthen ratus for conducting `these steps is -well kknown in the art and neednot be described... .The preliminary treatment fth caustic 4soda 'in this process apparently.' revents the fixing ofthe sulphur compounds'by the concen trat-ed fumingsulphuric acid, and a parentnd) the sulphur .containing constituents. ,x

The second and preferred method liminary treatment does not require liminary caustic sodaitreatmentof the oil` but the action is acocmplished `by the use of a phuric acid containing approximately. sulphuric acid, Valthough various stren hs of acid maybe used. The resulting aci is drawn* olf, the distillate neutralized by well known methods and introducedinto the 1 tatingtank2.-

It is understood that the` foregoing-de '4 `4 scribed process is only illustrative ofthe prenferred embodiment of my invention and my lnvention is'not limited to the preferred 4em- -xbodimen't but variousv changes maybe `made Y i inthe "recess such assubstitution of `other oxides. or the copper oxide without departlin from the spirit ofiny invention.`

invention 'is of the scopeset forthjin the filillowing claims. #I claim:

y 1. A process of jectin the oils to :the action of copperjozgldenn er the influence of 2.5,'1hejprocess of tillates"which includes agitating the 'dis-f l ight, with copper-` 3. Avprocess of purifying petnoleum oils 75.. effect o this preliminary treatment is appar.

thentreated separated from the oil, the""oil neutralized k and ,then introduced into the tank2.' Appaf purifying petroleum' oilsy x12-0 purifying petroleumdis i e. unstable sul:A 33.

phur containing constituents by treatment with sulphuric acid and caustic soda, treating said oils with copper oxide in the presence of light until the resultant action is complete, and separating the oil fromthe undissolved copper oxide and the dissolved copper compounds.

4. A process of treating a petroleum oil to remove from the oil those constituents which dissolve metals, which process includes subjecting the oil to the action of copper oxide carried out at a temperature substantially lower than the boiling temperature of the oil and under the influence of light, so that oil soluble compounds are formed with the copper oxide, and thereafter Separating from the admixture the purified 5. A process of renin petroleum oils which includes first removing from the oils sulphur compounds by treatment with sulphuric acid and a neutralizing agent, then subjecting the oil in the cold state to the action of copper oxide under the influence of light, and separating from the mixture 25 the puried oil.

Signed at El Segundo, Calif., this 7 th day of August, 1922.

` l RICHARD F. DAVIS. 

